DE-F-(05 J : pas Le Designation: D 1607 - 91 (Reapproved 2005) Standard Test Method for Nitrogen Dioxide Content of the Atmosphere (Griess- Saltzman Reaction)* This standard i issued under the fixed designation D 1607; the number immediately folowing the desgration indicates the year of naina adoption or, inthe case of revision, the year of last revaion. A number n parentheses indicates the year fast eapproval A superscript epsion (e) indicates an editor change snes te last revlon or reapproval, ‘his standara hes been approved for use by agentes ofthe Deparment of Delerse, 4. Scope 41.4 This test methods covers the manual determination of nitrogen dioxide (NO2) in the atmosphere in the ‘ange from 4 to 10 000 pg/ms(0.002 to ppm(y)) when sampling is conducted in fited-tip bubblers 41.2 For concentrations of NOzin excess of 10 mg/ma(6 ppm(v)), 8s occur in industrial atmospheres, gas bummer stacks, or automotive exhaust, of for samples relatively high in sulfur dioxide content, other methods should be applied. See for example Test Method 0 1608, 1.3 The maximum sampling period is 60 min at a flow rate of 0.4 Limin. 1.4 The values stated in SI units are to be regarded as standard. The values given in brackets are for information only 1.5 This standard does not purport to adress all ofthe safety concems, if any, associated with its use. Itis the responsibilty ofthe user ofthis standard to establish appropriate safety and health practices and determine the applicabilty of regulatory limitations prior to use. See also 7 2.2 for other precautions, 2. Referenced Documents 2.1 ASTM Standards: 9 © 1071 Test Methods for Volumetric Measurement of Gaseous Fue! Samples D 1198 Specification for Reagent Water 1356 Terminology Relating to Sampling and Analysis of Atmospheres 1357 Practice for Planning the Sampling of the Ambient Atmosphere D 1608 Test Method for Oxides of Nitrogen in Gaseous Combustion Products (Phenol-Disulfonic Acid Procedures) 1 3195 Practice for Rotameter Calibration © 3609 Practice for Calibration Techniques Using Permeation Tubes 1D 9631 Test Methods for Measuring Surface Atmospheric Pressure E 1 Specification for ASTM Liquid-in-Glass Thermometers E 128 Test Method for Maximum Pore Diameter and Permeability of Rigid Porous Filters for Laboratory Use 3. Terminology 3.1 For definitions of terms used in this test method, refer to Terminology D 1356. 4. Summary of Test Method 4.1 The NOzis absorbed in an azo-dye-forming reagent (1). red-violet color is produced within 15 min, the intensity of which is measured spectrophotometrically at 550 nm, 8. Significance and Use 5.1 Nitrogen dioxide plays an important role in photochemical smog-forming reactions and, in sufficient concentrations, is deleterious to health, agriculture, materials, and visibility 5.2 In combustion processes, significant amounts of nifric oxide (NO) may be produced by combination of atmospheric nitrogen and oxygen; at ambient temperatures NO can be converted to NOzby oxygen and other atmospheric oxidants. Nitrogen dioxide may also be generated from processes involving nitric acid, nitrates, the use of explosives, and welding6. Interferences 6.1 A ten-fold ratio of sulfur dioxide (S02) to NOz produces no effect. A thirty-fold ratio slowly bleaches the Color to a slight extent. The addition of acetone to the reagent retards the fading by forming a temporary addition product with SOs. This permits reading the color intensity within 4 to 5 h (instead of the 45 min required without the acetone) without appreciable losses. This test method is under the uracicton of ASTM Commitee D2 on Air Quay ands the cretresponsiity of Subsommitee D203 on ‘Ambient Atmospheres and Source Emissions. ‘Current ection approved Get. 1, 2008. Published January 2006, Orignaly approved in 1956. Last previous eon aeproved in 2000 a8 © 1807 - 01/2000) Adapted ftom “Selected Methods forte Measurement of At Polutans PHS Publication No 995-AP-11, May 1965. A smiar version hp been submit othe interscesety Commitee 3For referenced ASTM standart, visit the ASTM webste, vw astn.o¥, or contact ASTM Customer Senice a service@asin.org For ‘Annus Book of ASTM Siandards volume information, relerto the standars’e Document Summaly page an the ASTM wetate «The bolaface numbers in parentheses reer tothe lt of references append to his method. 6.2 A five-fold ratio of ozone to NOzwill cause a small interference, the maximal effect occuring in 3 h. The reagent assumes a slightly orange tint 6.3 Peroxyacety| nitrate (PAN) can produce @ color change in the absorbing reagent. However, in ordinary ambient air, the concentration of PAN is too low to cause any significant error in the, measurement of NOz 6.4 Interferences may exist from other nitrogen oxides and other gases that might be found in polluted air. 7. Apparatus 7.1 Sampling Probe—A glass or TF E-fluorocarbon (preferred) tube, 6 to 10 mm in diameter provided with a downwind facing intake (funnel or tip). The dead volume of the system should be kept minimal to avoid losses of NOzon the surfaces of the apparatus, 7.2 Absorber—An all-glass bubbler with a 60- um maximum pore diameter fit, similar to that ' a ' iMustrated in Fig. 1 eh 7.2.1 The porosity of the fritted bubbler, as well as the sampling flow rate, affect absorption efficiency. An efficiency of over 85 % may be expected with a flow rate of 0.4 Limin or less and a maximum pore diameter of 60 jum. Frits having a maximum pore diameter less than 60 um will have a higher efficiency but will require an inconvenient pressure drop for sampling, Considerably lower efficiencies are obtained with coarser frits 7.2.2 Measure the porosity of an absorber in ou accordance with Test Method & 128. If the ft W580 4 Ae is clogged or visibly discolored, carefully clean with concentrated chromic-sutfuric acid mixture, and rinse well with water and fedetermine the maximum pore diameter. Note 1—Caution: Do not cspose ofthis agent in the drain system. 7.2.3 Rinse the bubbler thoroughly with water and allow to dry before using 7.3 Mist Eliminator or Gas Drying Tube, filed with activated charcoal or soda lime is used to FIG. 1 Fritted Bubbler for Sampling Nitrogen Dioxide prevent damage to the flowmeter and pump, Ds 4 mie $F concenrmie mtn rae 1 sera ns tice ErLinoen 20 Ter eR aio outen neces AME Ntesewawaeaace 00 mi ue FRITTED CYLINCER, cevreneo i ruass Sor tow Pomgsity Is Tica MUST BE 0p, ax PORE ame ten7.4 Air-Metering Device—A calibrated, glass, variable-area flowmeter, or dry gas meter coupled with a flow indicator capable of accurately measuring a flow of 0.4 Limin. 7.8 Thermometer—ASTM Thermometer 33C, meeting the requirements of Specification & 1, will be Suitable for most applications of this test method 7.6 Manometer, accurate to 670 Pa (0.20 in. Hg). See Test Methods D 3631 7-7 Air Pump—A suction pump capable of drawing the required sample flow for intervals of up to 60 min is suitable, 7.8 Spectrophotometer or Colorimeter— An instrument suitable for measuring the intensity of absorptian at 550 nm, with stoppered tubes or cuvettes. The wavelength band-wiath is not eritical for this determination, 7.9 Stopwatch or Timer. 8. Reagents and Materials 8.1 Reagent grade chemicals shall be used in all tests. All reagents shail conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where such spectications are avallable.s Other grades may be used, provided itis frst ascertained that the reagent is of sufficiently high Punty to permit its use without lessening the accuracy of the determination. * 8.2 Punty of Water—Unless otherwise indicated, water shall be deionized water in accordance with ‘Specification D 1193 for Type | oF Il reagent water. Water shall be free of nitrite. 8.3 Absorbing Reagent—Dissolve 5 g of anhydrous sulfanilic acid (or 6.5 g of sulfanilic acid monohydrate) In almost a L of water containing 140 mL of glacial acetic acid. Gentle heating is permissible to speed up the process. To the cooled mixture, acd 20 mL of the 0.1 % stock solution of N-(1- naphthy/)- ethylenediamine dihydrochloride, and 10 mL of acetone. Dilute to 1 L. The solution will be stable for several ‘months if kept well-stoppered in a brown bottle in the refrigerator. The absorbing reagent shall be at room temperature before use. Avoid lengthy contact with air during preparation and use since discoloration of reagent will result because of absorption of NO2. 8.4 N-(1-Naphthy))-Ethylenediamine Dihydrochioride, Stock Solution (0.1 %)—Dissolve 0.1 g of the reagent in 100 mL of water. Solution will be stable for several months if kept well-stoppered in a brown bottle in the ‘efrigerator. (Alternatively, preweighed amounts of the solid reagent may be stored.) 8.5 Sodium Nitnte, Standard Solution (0.0246 g/L)—One ml. of this working solution of sodium nitrite (NaNO2) produces a color equivalent to that of 20 ug of NOzin 1 L of air at 101 kPa (29.92 in, Hig) and 25°C (see 10.1), Prepare fresh just before use by dilution from a stock solution containing 2.46 g of the reagent grade granular solid per litre. Assay the solid reagent. The stock solution is stable for 90 days at room temperature, and for 1 year in a brown bottle under refrigeration 8.6 NO2 Permeation Device—With a permeation rate of 0.1 to 0.2 ygimin. «Reagent Ghemicels, American Chemical Society Spacifcalons, American Chemical Society, Washington, OC. For suggestions onthe testing ftreagents not 'ieted by the American Chemical Sacely, see Analar Standars for Laboraty Chemicals, BDH Lid, Poole, Dorset. UK. andthe United ‘Staios Phormacopsia and Netonai Formulary, U8. Phammacopeial Conventan. Ine (USPC), Rocke, 9. Sampling 9.1 Sampling procedures are described in Section ‘1. Different combinations of sampling rates and time ‘may be chosen to meet specific needs, but sample volumes and air flow rates shall be adjusted so that, linearity is maintained between absorbance and concentration aver the dynamic range. 9.2 See Practice D 1357 for sampling guidelines. 10, Calibration and Standardization 10.1 Sampling Equipment. 10.1.1 Flowmeter—Calibrate flowmeter prior to use, using Practice D 3195. 10.1.2 Gas Meter—Calibrate gas meter prior to use, using Test Method D 1071 10.2 Analysis. 10.2.1 Recommended Procedure: 10.2.1.1 The recommended procedure for preparation of calibration standards is by the use of permeation devices (3). Analysis of known concentrations gives calibration curves that simulate all of the operational Conditions performed during sampling and analytical procedures. 10.2.1.2 Using the apparatus described in Practice D 3609, generate a gas stream of known concentration Sample it asGescribed in 11.1, five times, adjusting the sample times so that the amount of NOzin each collected. Sample solution covers the dynamic range of the method. Analyze each as described in }|.2, and prepare @ calibration curve using regression analysis by the method of least squares, Determine {he reciprocal of the slope of the line, and denote it as K, the volume of NOz, in uL, intercepted at an absorbance of 1.0. 10.2.2 Altemate Procedure: {0.2.2.1 Standardization is based upon the empirical observation (1, 2, 5) that 0.82 mol of NaNOz produces {he same color as 1 mol of NOz. One mL of the working standard solution contains 24.6 ug of NaNO> Since the molecular weight of NaNOais 69.1, this is equivalent to (24.6) 69.1) x (46.0/0.82) = 20 ig NO2. 10.2.2.2 For convenience, standard conditions are taken as 101 kPa (29.92 in. Hg) and 25°C, at which the ‘molar gas volume is 24.47 L. This is very close to the standard conditions used for air-handiing equipment {101 kPa (29.92 in. Hg), 70°F [21.1°C], and 50 % relative humidity, at which the molar gas vohime is 24.76 {or 1.2 % greater. Ordinarily, the correction of the sample volume to these standard conditions i slight and may be omitted, however, for greatest bias, it may be made by means of the perfect gas equation 10.2.2.3 Add graduated amounts of NaNO solution up to 1 mL (measured accurately in a graduated pipet oF small buret) to 2 series of 25-mL volumetric flasks, and dilute to the marks with absorbing reagent. Mix allow 15 min for complete color development, and read the absorbance (see / 2) 10.2.2.3.1 Good results can be obtained with these small volumes of standard solution i they are carefully measured, Making the calibration solutions up to 25-mL. total volume, rather than the 10-mL volume used for samples, increases accuracy 10.2.2.3.2 Plot absorbances of the standards against micrograms of NO2 per mL of absorbing reagent. The Plot follows Beers law. Find the standardization factor, K, as described in 10.2 1.1 11, Procedure 111 Assemble in order as shown in Fig. 2, a sampling probe (optional), trted-tip absorber, mist eliminator or trap, flowmeter, and pump. Measure temperature and pressure difference from almospheric so that Corrections for gas volume may be applied. Keep the flowmeter free from spray or dust. Use ground-glass Connections, Buttto-butt glass connections with vinyl tubing also may be used for connections without losses if lengths are kept minimal 11.2 Pipet 10.0 mL of absorbing reagent into a dry fritted bubbler. Draw an air sample through it at the rate of 0.4 Limin, long enough to develop sufficient final color (about 10 to 60 min). Note the total alr volume sampled. Measure and record air temperature and pressure. After using the bubbler, rinse well wth water and dry. If fitted tip is visibly discolored, clean in accordance with the procedure in 7.2 > 11.3 after sampling, development of the red-violet color is complete within 15 min at room temperatures. Transfer to a stoppered cuvette and read in a spectrophotometer at 550 nm, using distilled water as a Feference. Deduct the absorbance of the reagent blank from that of the sample, 41.4 Colors too dark to read may be quanttatvely diluted with unexposed absorbing reagent. Then multiply the measured absorbance by the dilution factor, Devine “URE ist ct NaToR ory rest eres | MANOWETER FIG. 2 Sampling Train12. Calculation 12.1 Air Volume—Convert the volume of air sampled to the volume at standard conditions of 25° C and 101.3 KPA (1 atm), as follows: Va= [Vx P/101.3] x [298.15/7] (1) Where: Ve volume of air sampled at standard conditions, L v volume of air sampled at ambient conditions, L Pp average ambient atmospheric pressure, kPa iy T = average ambient atmospheric temperature, K 101.3 = pressure of standard atmosphere, kPa, and 290.15 = temperature of standard atmosphere, K 12.2 Compute the concentrations of NO2in the sample as follows: NO,, ugim? = (absorbance x K x 10° x w/V, * (2) Where: K standardization factor (micrograms of NO2 per mL of absorbing solution/absorbance), ra /olume of air sample, L (see 12.1), 10° Ume, and v= volume of absorbing reagent, mL. 13. Precision and Bias 13.1 The information in this section is derived from the data collected and analyzed as part of ASTM “Project Threshold" (4). 13.2 Repeatability (Single-Analyst)—The standard deviation of results obtained by a single analyst on ‘separate samples from the same flowing air stream is also shown in Fig. 3 as a function of the mean value Of NO2 determined, The range of data used is 10 to 400 yg/ms. Duplicate analyses should be considered Suspect (95 % confidence level) if they differ by more than 2.89 times the standard deviation of repeatability. 13.3 Reproducibility (Multiaboratory)—The standard deviation of single analyses, obtained by analysts {rom different laboratories taking separate samples from the flowing air stream, is plotted in Fia. 3 against the mean value of NOz determined. The range of data used is 16 to 400 ygims. Duplicate values should be Considered suspect (95 % confidence level) if they differ by more than 2.81 times the standard deviation of reproducibility 13.4 Bias—Although the measurement of bias was designed to produce data that described the bias of this method, no generally applicable statements regarding bias can be made. ‘Table 1 gives the average bias found at each of the three locations used during the interlaboratory test program, The method of evaluating bias consisted of adding @ known amount of NOzgas to a sample Stream and determining the percent recovery on the basis of simultaneous analyses of spiked and “unspiked” samples. Bias is the difference between the determined recovery and 100 %. 13.6 The method for determining the bias detects only those errors that are proportional to the NO2|ev fixed errors are cancelled in the subtraction process. Fixed errors shall refer to interferences. For this. reason, bias is expressed in percentage terms rather than in absolute units 13.6 Based on the data in Table 1, itis clear that the bias found in Manhattan, NY, is significantly higher than that found in Los Angeles, CA, or Bloomington, IL. This difference in bias is not due to the fact that the average NOz levels found in Manhattan were higher than those found at the other two sites (4). The ference in bias may be caused by other interfering substances, such as NO or other nitrogen oxides, but these data alone are not conclusive. 14. Keywords 14.1 ambient atmospheres; analysis; colorimetric analysis; Griess-Saltzman Reaction; nitrogen dioxide: samplingLocation Mean Degrees ‘Mean NO2 Uncertainty Bias of Freedom Measured of mean (95 % Confidence) Los Angeles,cA | +11% = 150 ygim? 210% | Bloomington, IN “1% 50 ugim® __ 210% New York, NY $35.% 70 210 pghm® 10% ‘TABLE 1 Bias Found in NO: Measurement Found During Project Threshold (6) 5 sopiey $8 snore se 3 = Ye Nee 3 nay ceNceNT MATION FIG, 3 Repeatability and Reproducibility (6) are REFERENCES (1) Seltzman, 8. ., "Colorimetric Microdetemmination of Nitrogen Dioxide in the Atmosphere,” Analytical Chemistry, Vol 26, 4954, pp. 1949-85, (2) Scaringeli, F. P., Rosenberg, E., and Rehme, K, A. "Comparison of Permeation Devices and Nitite Ion as Standards for the Colorimetric Determination of Nragen Dioxide,” Environmental Science and Technology, Vol 4, 1970, pp, 924-9, (3) Oeete, A. E., and Ortman, G. C., "Primary Standards for Trace Gas Analysis,” Anajtical Chemistry, ANCHA, Vol 28, 1966, pp. 760-3. (4) Foster, JF. and Beatty, G. H., “Final Report on intertaboratory Cooperation, Study of the Precision and Accuracy ofthe Measurement of Ntrogen Dione Conentin the Amosphere Using ASTM Method D 1607, atele, Climbus Laboratories, olumbus, Ohio, 1973, (5) Research Report No, 0-22-1019 is availabe from ASTM Headquarters, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2969. ‘ASTM Intemational takes no position respecting the validity of any patent rights asserted in connection with any item ‘mentioned in this standard. Users of this standard are expressly advised that determination of the valty of any such patent rights, and the risk of infingement of such rights, are entirely their own responsibilty. 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